Process for the treatment of vegetable fibers and artificial threads



Patented Jan. 2, 1940 PROCESS FOR THE TREATMENT OF VEGE- TABLE FIBERS AND ARTIFICIAL THREADS Leon Lilienfeld, Vienna, Austria; Paul Abel, Vienna, Austria (Germany), executor or incase of his inability to act, Emerich Hunna, Vienna, Austria (Germany), and Antonette Lilienfeld, Vienna, Austria heir (Germany), sole No Drawing. Application June 22, 1932, Serial No. 618,803. In Great Britain July 4, 1931 18 Claims.

My invention relates to a process for treating vegetable fibers, such as cotton, and artificial threads for the purpose of amplifying their dyeing properties.

I have discovered that improved fibers are obtained which, in contradistinction to the original fibers, exhibit aflinity to acid dyestuffs and, in some cases, also to those special dyestuffs. which are employed in the dyeing of artificial threads produced from fatty acid esters of cellulose, such as cellulose acetate silk, when vegetable fibers or artificial threads or filaments are, in absence or presence of a basic substance or a catalyser, treated with one or more organic compounds having an aliphatic nucleus, and which contain (in said aliphatic nucleus) at least one nitrogen atom attached to a carbon atom and at least one oxygen atom attached to a carbon atom and at least one halogen atom attached to a carbon atom, wherein, if each of these three different elements is contained only once in the molecule, not more than two of them are attached to one and the same carbon atom and, if one or two or all three of these difierent elements are contained more than once in the molecule, there is among them at least one nitrogen atom and at least one oxygen atom and. atleast one halogen atom which are arranged in such a manner that not more than two of these three different kinds of atoms are attached to one and the same carbon atom whilst the third is attached to another carbon atom.

Among the reagents characteristic of the invention, I prefer organic compounds in an aliphatic nucleus of which at least one nitrogen atom is attached to a carbon atom and at least one oxygen atom is attached to another carbon atom and at least one halogen atom is attached to a third I carbon atom.

Many halogen derivatives of nitroor aminopropanols or their homologues are especially recommended in the present process.

Instead of the compounds set forth above, their derivatives, such as esters or ethers or N-substitution'products or. (in the case of unsaturated compounds) addition'derivatives can also be employed in the present invention.

Besides nitrogen (or a group containing nitrogen) and oxygen and halogen, the reagents characteristic of the present invention may contain sulphur or a group containing sulphur.

Instead ot the compounds themselves, substances or mixtures of substances capable of giving rise to the formation of the compounds characteristic of the present invention may be used, for instance, where in the subjoined examples it is stated that one of the compounds of the examples described in my U. S. application Ser. No. 618,800 may be used, there may be substituted the use of diluted or undiluted u-dichlorohydrine and an alcoholic or aqueous solution of ammonia so that these react with each other to form the body which is the effective agent of the invention.

According to the present state of my knowledge, all the halogenated compounds of an aliphatic nucleus containing one or more nitrogen atoms and one or more oxygen atoms referred to and particularly set forth in theexamples and in the descriptive part of my U. S. patent application Ser. No. 618,801, Pat. No. 2,051,051 are suitable for the present invention, U. S. patent application Ser. No. 618,800 included. A substitute application for 618,800 was filed on which Patent No. 2,167,661 was issued, and a division of 618,800 was filed on which Patent No. 2,167,807 was issued.

For more completely describing the treating reagents of the present case, and the modes of producing same, the following examples are here copied from the said concurrent application 618,800. Example A and the clear alcoholic filtrate, together with the washing alcohol, is freed from alcohol and ammonia by distillation under reduced pressure at 30to 35 C.

The residue is a clear, yellow, very viscous oil, soluble in water and alcohol, but insoluble in ether.

In modified forms of this process, other amounts of the alcoholic ammonia solution'can be used, to 1000 parts of the dichlorhydrine, (instead of the 1185 parts given above) e. g. from 170 parts to 2720 parts of the alcoholic solution of ammonia,-

prepared as indicated above (and which contains about 19.4% of NH3) or 7400 parts of a 4% alcoholic ammonia solution, can be used. The time and temperature of reaction can be modified,

e. g. from three hours at 50-75% C., to days in the cold.

Example B 1000 parts of a-dichlorohydrine are cooled down to 0 C. whereupon dry gaseous ammonia is introduced until the reaction mass weighs 1080 to 1085 parts. v

The reaction mass is allowed to stand at room temperature for about 20 to 24 hours during which time one of the taps with which the vessel is fitted, remains open.

After that time, the reaction mass is again cooled down to 0 C. and gaseous ammonia introduced until the reaction mass weighs 1170 to 1180 parts, whereupon the vessel is allowed to stand in the refrigerator over night with one of the taps open. During this time, the amount of the separated crystals of ammonium chloride shows a distinct increase. Since part of the introduced ammonia escapes during standing on ice, after that time, the total weight of the reaction mass is 1140 I to 1145 parts.

This procedure is further repeated another four times, the weights of the reaction mass being as follows:

Third day.-Weight of the mass immediately after the introduction of the gaseous ammonia: 1180 to 1190 parts.

Weight of the reaction mass after standing over night on ice: 1150 to 1160 parts.

Fourth day.Weight of the reaction mass immediately after the introduction of the gaseous ammonia: 1190 to 1195 parts.

Weight of the reaction mass after standing over night on ice: 1190 to 1195 parts (no decrease).

Fifth day.--Weight of the reaction mass imme diately after the introduction of monla: 1195 to 1200 parts.

Weight of the reaction mass after standing over night on ice: 1190 to 1195 parts (slight decrease).

Sixth day.-Weight of the reaction mass immediately after the introduction of the gaseous ammonia: 1210 to 1220 parts.

Now the reaction mass is freed from the excess of ammonia by blowing through a current of air for 4 hours, the final weight being 1175 to 1180 parts.

Now the product of the reaction is freed from the crystals by filtration and then kept under reduced pressure at room temperature in order to remove the last traces of ammonia.

The final product is a viscous, clear oil that is soluble in water and alcohol. In standing at room temperature for a longer time, it has a tendency to become turbid or even of depositing crystals which are probably ammonium chloride.

Instead of the glycerine dichlorhydrin, equivalent quantities of dibromhydrine or similar iodine compounds, or equimolecular proportions of other unsubstituted dihalogenhydrines of polyhydric alcohols can be used. Erythrite dichlorohydrine, mannite dichlorohydrine, can be used in like manner.

The products can be purified (removing the byproducts) by distillation under vacuum, or washing with ether, etc.

In addition to the characteristic nitrogen-containing groups, oxygen-containing groups, and

the gaseous amhalogen, distributed as described above, the substances used in the present invention (as described in Ser. No. 618,801) can also contain other groups or radicals, such as nitroor amino-derivatives of oxy or oxo-compounds and among these halogen derivatives of oxyamines, that is compounds which contain at least one substituted or unsubstituted amino-group and at least one substituted or unsubstituted hydroxyl group and at least one halogen atom and, according to the present state of my knowledge, among these, halogen derivatives of amino-derivatives of propanols or of homologues of propanols give good results in the present process.

The reaction products, produced as above described, are or contain, in many cases, unsaturated compounds, and the products of the action of these reagents on cotton, cellulosic artificial threads etc., are also unsaturated compounds.

Instead of the compounds set forth above, their derivatives, such as esters or others or N-substitution products or (in the case of unsaturated compounds) addition derivatives can also be used.

Besides nitrogen (or a group containing nitrogen) and oxygen and halogen, the reagents to be contactedwith vegetable textiles or with artificial thread textiles in the present process may contain sulphur or a group containing sulphur.

' Instead of the reagents mentioned above, other agents of the types mentioned may be used (for contactingwith the textile material), for instance 2-chloro-2-nitro -propanol--(1) or 2-bromo-2- nitro-propanol-(l) l-bromo lnitro-propanol- (2) 3:3:3-trichloro 1 nitro propanol, acetimido-fl-chloro-ethyl ether, dibromo-acetic acid dimethyl-amide, N-methyl-N-chioro-acetyl-urea, dichloro-acetic acid ethyl-'amide, oxalic acid ethyl ester-[c bromo-ethyl-amide], N-[/9,'y-dibromopropyll-urea, acetic acid [,B -dibromo-propylamide], trimethyl-[iodoxy-propyl] ammonium hydroxide, chlor-acetyl-amino-acetic acid ethyl ester, chloracetyl-diglycine-amide, oz-fi-dibIOIIlO- propionyl-amino acetic acid, ,o-chlor-a-aminopropionic acid, chlor-allyl-phenyl-urea, [2-

bromo-methyl-benzyll-o-anisidine, 2-l' -chlor-fl-A5 The fibrous textile material may be exposed to' the treatment according to the present invention in the original state or after having been pretreated by any known method, for example with acylating agents, such as organic acid anhydrides in the presence or absence of catalysers, or with strong organic or mineral acids, or with acid halides, or with sulpho-acid halides, or with phosphorus halides or the like.

The textile material may be pretreated, by any process known in the textile industry, for example a treatment in known manner with mercerizing reagents.

The treatment according to the invention may be carried out at room temperature or at a temperature below room temperature, or at an elevated temperature, for example at about 60 C. to C. more or less. But these temperatures are given only by way of example, and higher temperatures (when using substances which are stable at the higher temperatures) can be empioyed.

' Example 1 Cotton yarn or cotton fabric or viscose silk or viscose Lilienfeld-silk or cuprammonia silk or denitratednitrate silk or acetate silk or ethyl cellulose s'ilk of low degree of ethylation is, optionally after having been wetted according to any one of the known wetting processes, immersed in an aqueous solution of to per cent. strength of oneof the compounds of the examples described in my U. S. patent application Ser. No. 618,800 or of one of the other compounds proposed for contacting with viscose in any one of the examples of my U. S. patent application Ser. No. 618,801. In the said applications 618,800 and 618,801 (both filed June 22', 1932) I have described and claimed the treatment of a halohydrine (or analogous ester) with. ammonia whereby highly useful organic bodies are formed,- which can also be added to viscose, these bodies having apparently the chemical composition describedabove. The said compounds are comewhat complex organic bodies. After having remained in this solution for 6 hours at 20 C. the textile material is washedand dried.

The product shows a distinct afllnity for acid colours. The product of this example (as well as the products of the other examples in said application 618,800), upon being decomposed with strong hydriodic acid, yield alkyl iodide. If the nitrogen-halogen-oxygen compound employed (of the-type above described as characteristic of this invention) is a derivative of glycerine, then the decomposition'of the product with hydriodic acid will produce C 3H7I.

Example 2 Mode of procedure as in Example 1, but with the diiference that, after the impregnating step, thematerial is not washed, but only dried, or dyed direct without drying.

Example 3 The process is conducted as in Example 1 or 2, but with the difference that the treatment with the solution of the nitrogen body is conducted at 100 to 120 C.

Example 4 I The process is conducted as in Example 1 or 2,

but with the difference that the treatment with the solution of the nitrogen body is conducted at 180? C., for from 10 minutes to 2 hours.

Example 5 100 parts of cotton yarn or cotton fabric or viscose silk or viscose Lilienfeld-silk or cuprammonia silk or denitrated nitrate silk or acetate silk or ethyl cellulose silk of a low degree of ethylation are introduced into 2000 parts of caustic soda solution of 18 per cent. strength. After 3 hours the excess of the caustic soda solution is removed by centrifuging or pressing and the goods are introduced into a solution of 20 to 30 per cent. strength of one'of the aliphatic compounds described in my U. S. patent application Ser. No. 618,800 in acetone of 90 per'cent. strength where they remain for 2 to 3 hours. They are then washed with water and, optionally after acidification and washing, dried.

viscose Lilienfeld-silk or cuprammonium. silk or Example 6 The process is conducted as in Example 5, but

with the diiference that, instead of the causticsoda solution of 18 per cent. strength, a caustic soda solution of 30 per cent. strength is used.

Example 7 The process is conducted as in Example 5 or 6, but with the difference that the treatment is conducted at 60 to 70 C.

Example 8 The process is conducted as in any one of the Examples 5 to 7, but with the difference that, instead of the aqueous caustic soda solution an strength is used.

Example 9 The process is conducted as in any one of the Examples 5 to 7, but with the .diflference that, instead of the aqueous caustic soda solution, an 18 or 30 per cent. solution of caustic soda in alcohol of 60 per cent. strength is used.

Example 10 The process is conducted as in any one of the preceding examples, but with the difierence that the cotton yarn or cotton fabric or viscose silk or denitrated nitrate silk or acetate-silk or-ethyl cellulose silk of a low degree of ethylation is, in known manner, pre-treated with a phosphorus halogen compound in presence of alkali.

Example 11 The process is conducted as'in any one of the preceding examples, but with the difference that the material is, iIl-kIIOWII manner, pre-treated with p-toluene-sulpho-chloride in presence of 0 pyridine.

Example 12 The process is conducted as in any one of the I preceding examples, but with the difference that the material is, in known manner, pre-treated with ptoluene-su1pho-chloride in presence of caustic soda.

- Example 13 The process is conducted as in any one of the preceding examples, but with the difference that the material is, in known manner, pre-treated with benzoyl chloride.

In the foregoing examples, instead of the nitrogen compounds employed therein, any one of the aliphatic compounds containing nitrogen and oxygen and halogen referred to. or specifically named in my U. S. patent application Ser. No. 618,801 can be used. 1

Wherever the context permits, the term fabrics (for example pure cotton fabrics) or mixed fabrics or in the loose, unspun form or in the form I of spun goods, such as yarn in skeins, cops, or

warps. The term artificial threads" denotes artificial l6 alcoholic caustic potash solution of 10 per cent. i

threads and spun and woven goods (including pure and mixed fibers and .fabrics) of all kinds, for instance artificial silk, staple fiber, artificial cotton, artificial wool, artificial hair and artificial straw of any kind.

The term cellulosic textile fibers" denotes textile vegetable fibers and artificial threads, as defined in the last two paragraphs, the term cellulosic denoting that the fibers, threads, etc., contain cellulose or a compound of cellulose.

The term propanol compound" is intended to embrace propanols and homologues of the same.

The term organic derivative is intended to embrace esters, ethers, N-substitution products and (in the case of unsaturated compounds) addition derivatives.

What I claim is:

1. A process of improving cellulosic textile fibers which comprises treating same with at least one organic compound which contains an aliphatic chain of carbon atoms connected carbon-to-carbon and which aliphatic chain contains chemically combined halogen, oxygen 4 and nitrogen, each bonded to a difierent carbon atom in said chain.

2. A process of improving cellulosic textile fibers which comprises treating same with at least one organic compound which contains an aliphatic chain of carbon atoms connected carbon-to-carbon andwhich compound contains at least one amino group and at least one hydroxyl group and at least one halogen element, each of said substituents being bonded to a different carbon atom in said chain.

3. A process of improving cellulosic textile fibers which comprises treating them with at least one halogen derivative of an amino-derivative of a propanol compound.

4. A process as claimed in claim 1, wherein the organic compound used is a soluble reaction product of ammonia on a dilialohydrine of glycerine.

5. A process of improving cellulosic textile fibers which comprises treating same in presence of a basic substance with at least one organic compound which contains an aliphatic chain of carbon atoms connected carbon-to-carbon and which compound contains at least one amino group and at least one hydroxyl group and at least one halogen element, each of said substituents being bonded to a different carbon atom in said chain.

6. A process of improving cellulosic textile fibers which comprises treating same in presence of caustic alkali with at least one organic compound which contains an aliphatic chain of carbon atoms connected carbon-to-carbon and which compound contains at least one amino group and at least one hydroxyl group and at least one halogen element, each of said substituents being bonded to a different carbon atom in said chain.

7. A process of improving cellulosic textile fibers which comprises treating them with at least one halogen derivative of an amino-derivative of glycerine.

8. Aprocess of improving cellulosic textile fibers which comprises treating them in presence of a basic substance with at least one halogen derivative of an amino-derivative of glycerine.

9. A process of improving cellulosic textile fibers which comprises treating them in presence of caustic alkali with at least one halogen derivative of an amino-derivative of glycerine.

10. A process which comprises treating cellulosic textile fibers with a halogen-containing organic reaction product of ammonia upon a dihalohydrine.

11. A process of improving cellulosic textile fibers which comprises treating them in presence of a caustic alkali with at least one halogen derivative of an amino-derivative of a propanol compound.

12. A process as claimed in claim 10, wherein, instead of adding the pre-formed organic compound defined in the said claim, such organic compound is produced in intimate contact with said cellulosic textile fibers by a chemical reaction.

13. A process which comprises treating cellulosic textile fibers in presence of a caustic alkali with a halogen-containing organic reaction product of ammonia upon a dihalogenhydrine.

14. As new products, cellulosic textile fibers which, owing to an after-treatment, contain, in a radical replacing a hydroxyl hydrogen atom of cellulose, at least one amino group and at least one oxygen atom, each being bonded to a different carbon atom, and which fibers dye with acid and substantive dye-stufis,

15. As now products, cellulosic textile fibers which. owing to an after-treatment, contain, in a radical replacing a hydroxyl-hydrogen atom of cellulose, unsaturated constituents, at least one which, owing to an after-treatment, contain, in a I radical replacing a hydroxyl-hydrogen atom of cellulose, at least one amino group and at least one oxygen atom, each being bonded to a difierent carbon atom, and which products dye with acid, substantive and cellulose acetate dye-stuffs. 18. As new products, cellulosic textile fibers which, owing to an after-treatment, contain unsaturated constituents and nitrogen both in a polyvalent aliphatic radical which is in chemical combination with a cellulose residue, and which fibers dye with acid and substantive dye-stufis.

LEON IJIIENFELD. 

